CN113717639A - Polysilazane high-temperature resistant paint for carbon fiber composite material and preparation method thereof - Google Patents

Polysilazane high-temperature resistant paint for carbon fiber composite material and preparation method thereof Download PDF

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CN113717639A
CN113717639A CN202111080275.7A CN202111080275A CN113717639A CN 113717639 A CN113717639 A CN 113717639A CN 202111080275 A CN202111080275 A CN 202111080275A CN 113717639 A CN113717639 A CN 113717639A
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temperature resistant
carbon fiber
polysilazane
resistant coating
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张志敏
常明月
刘章友
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Kuberd Chemical Shanghai Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/70Additives characterised by shape, e.g. fibres, flakes or microspheres

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Paints Or Removers (AREA)

Abstract

The invention discloses a polysilazane high-temperature resistant coating for a carbon fiber composite material and a preparation method thereof, wherein the high-temperature resistant coating comprises 30-40 parts of organic silazane resin, 45-60 parts of butyl acetate, 12-20 parts of high-temperature resistant pigment, 2-5 parts of anti-settling agent, 1-2 parts of fumed silica and 1-2 parts of dispersing agent. When the high-temperature resistant coating is coated on the surface of the carbon fiber composite material, the coating does not change color, crack or fall off when heated in a muffle furnace at 800 ℃ for 1 h. The organic silazane resin can be subjected to ceramic conversion at high temperature to produce a cross-linked network of silicon nitride, silicon oxide and the like, and has excellent physical properties of high temperature resistance, wear resistance and the like, and the corrosion resistance and high temperature resistance of the coating are further improved by adding the components of silicon dioxide and the like. The polysilazane is applied to the high-temperature resistant coating, so that the chemical stability, the thermal stability and the application temperature of the carbon fiber can be better reflected.

Description

Polysilazane high-temperature resistant paint for carbon fiber composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of high-temperature resistant coatings, and particularly relates to a polysilazane high-temperature resistant coating for a carbon fiber composite material and a preparation method thereof.
Background
The carbon fiber industry develops rapidly, has great application requirements in many fields, and with the development of the carbon fiber industry, other materials such as epoxy, polyurethane and other resins cannot meet the high temperature resistance requirement of the carbon fiber, so that the carbon fiber material cannot well embody the advantages of the carbon fiber material. The organosilicon coating which is applied more currently is a coating which takes organosilicon resin siloxane as a main film forming substance, has excellent performances of heat resistance, radiation resistance, water resistance, chemical corrosion resistance, electric insulation and the like, and is developed rapidly in recent years. But the heat-resisting temperature of the prior pure organic silicon resin is lower, only about 300 ℃, can reach 400-500 ℃ after being added with high-temperature-resistant pigment and filler, and the coating is easy to generate the phenomena of color change, cracking, falling off and the like at the higher temperature of 800 ℃. Based on the above-mentioned defects in the prior art, there is a need to develop a coating capable of resisting high temperature of above 800 ℃ to meet the market demand.
Disclosure of Invention
The invention provides a polysilazane high-temperature resistant coating for a carbon fiber composite material and a preparation method thereof, aiming at overcoming the defects in the prior art.
The invention is realized by the following technical scheme: the invention discloses a polysilazane high-temperature resistant coating for a carbon fiber composite material, which is composed of the following raw materials in parts by weight: 30-40 parts of organic silazane resin, 45-60 parts of butyl acetate, 12-20 parts of high-temperature resistant pigment, 2-5 parts of anti-settling agent, 1-2 parts of fumed silica and 1-2 parts of dispersing agent.
As a preferred embodiment of the invention, the polysilazane high-temperature resistant coating for the carbon fiber composite material consists of the following raw materials in parts by weight: 32 to 38 portions of organic silazane resin, 48 to 55 portions of butyl acetate, 14 to 18 portions of high-temperature resistant pigment, 3 to 4 portions of anti-settling agent, 1.2 to 1.7 portions of fumed silica and 1.3 to 1.8 portions of dispersant.
As the best mode for carrying out the invention, the polysilazane high-temperature resistant coating for the carbon fiber composite material consists of the following raw materials in parts by weight: 35 parts of organic silazane resin, 50 parts of butyl acetate, 16 parts of high-temperature resistant pigment, 3 parts of anti-settling agent, 1.5 parts of fumed silica and 1.5 parts of dispersing agent.
The invention also discloses a preparation method of the polysilazane high-temperature-resistant coating for the carbon fiber composite material, which specifically comprises the following steps:
the method comprises the following steps: weighing the raw materials according to the weight parts of the components of the raw materials in the coating, then respectively placing the pigment and the filler in a dry and clean tray, placing the tray in a vacuum oven for drying, respectively bagging and sealing after natural cooling for later use, and carrying out corresponding identification;
step two: adding the organic silazane resin and the dispersing agent into a charging basket, adding part of the solvent, stirring for 15min at a low speed by using a high-speed stirrer, and adding the raw materials dried in the step one after uniform dispersion;
step three: stirring for 30min at the rotating speed of 1200-1500 r/min by using a stirrer, uniformly dispersing, grinding until the fineness of the coating is below 30 micrometers, adjusting the viscosity to 10-20 s by using the residual solvent, detecting by using a coating-4 cup, filtering and packaging after the viscosity is detected to be qualified.
The organic silazane resin used in the present invention is produced by Kubei chemical (Shanghai) Co., Ltd. The high-temperature resistant pigment SP-1005 is purchased from Shanhai chemical pigment Co., Ltd, Shenzhen city. Butyl acetate was purchased from Shanghai salary chemical Co., Ltd. The Haiming Si anti-settling agent 201P is purchased from Jintenglong industry Co., Ltd, Shenzhen city. Fumed silica HT-200 is available from Kjen chemical Co., Ltd. Dispersant WE-D2645R was purchased from Anhui Kangnuo chemical Co., Ltd.
The application method of the polysilazane high-temperature resistant coating for the carbon fiber composite material comprises the following steps: firstly, polishing the surface of a base material of the carbon fiber composite material, then uniformly mixing the high-temperature resistant coating, uniformly spraying the mixture on the surface of the carbon fiber composite material, heating the mixture for 1 hour at the temperature of 250 ℃, and then heating the mixture for 1 hour at the temperature of 500 ℃ until the mixture is completely cured.
The invention has the beneficial effects that: the invention mainly aims at the defect of poor heat resistance of the traditional high-temperature resistant organosilicone siloxane coating and provides a high-temperature resistant coating for the surface of a carbon fiber composite material and a preparation method thereof. When the polysilazane high-temperature resistant coating prepared by the method is coated on the surface of a carbon fiber composite material, the coating does not discolor, crack or fall off under the condition of heating for 1 hour in a muffle furnace at 800 ℃. The organic silazane resin used in the high-temperature resistant coating can generate ceramic conversion at high temperature to produce a cross-linked network of silicon nitride, silicon oxide and the like, and has excellent physical properties of high temperature resistance, wear resistance and the like, and the corrosion resistance and the high temperature resistance of the coating are further improved by adding components such as silicon dioxide and the like. The invention applies polysilazane in the field of high temperature resistant coating, and can better reflect the chemical stability, thermal stability and application temperature of carbon fiber. The polysilazane high-temperature resistant coating is repeatedly verified at the client at present, and the result shows that the high-temperature resistant coating can meet the requirements of high strength, high hardness and high temperature.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The parts by weight of each raw material component of the high temperature resistant coating in examples 1 to 3 of the present invention are shown in table 1.
Table 1: the weight parts of each raw material component in examples 1 to 3.
Figure BDA0003263718650000031
Figure BDA0003263718650000041
The preparation method of the polysilazane high-temperature resistant coating for the carbon fiber composite material in the embodiments 1 to 3 of the invention comprises the following steps: the method comprises the following steps: weighing the raw materials according to the weight parts of the components of the raw materials in the coating, then respectively placing the pigment and the filler in a dry and clean tray, placing the tray in a vacuum oven for drying, respectively bagging and sealing after natural cooling for later use, and carrying out corresponding identification; step two: adding the organic silazane resin and the dispersing agent into a charging basket, adding part of the solvent, stirring for 15min at a low speed by using a high-speed stirrer, and adding the raw materials dried in the step one after uniform dispersion; step three: stirring for 30min at the rotating speed of 1200-1500 r/min by using a stirrer, uniformly dispersing, grinding until the fineness of the coating is below 30 micrometers, adjusting the viscosity to 10-20 s by using the residual solvent, detecting by using a coating-4 cup, filtering and packaging after the viscosity is detected to be qualified.
Comparative example 1: an organic silicon high-temperature resistant coating is prepared from the following components in parts by weight: 30 parts of organic silicon (siloxane) resin, 45 parts of butyl acetate, 12 parts of high-temperature resistant pigment, 2 parts of anti-settling agent, 1 part of fumed silica and 1 part of dispersing agent. The preparation method of the organosilicon high-temperature resistant coating in the comparative example 1 comprises the following steps: adding organic silicon (siloxane) resin and a dispersing agent into a charging basket, adding a part of solvent, stirring for 15min at a low speed by using a high-speed stirrer, adding pigment and filler raw materials after uniform dispersion, stirring for 30min at a rotating speed of 1200-1500 r/min, grinding until the fineness of the coating is below 30 micrometers after uniform dispersion, adjusting the viscosity to 10-20 s by using the residual solvent, coating in 4 cups for detection, filtering and packaging after qualified detection.
Comparative example 2: an organic silicon high-temperature resistant coating is prepared from the following components in parts by weight: 40 parts of organic silicon (siloxane) resin, 60 parts of butyl acetate, 20 parts of high-temperature resistant pigment, 5 parts of anti-settling agent, 12 parts of fumed silica and 2 parts of dispersing agent. The preparation method of the organosilicon high-temperature resistant coating in the comparative example 2 comprises the following steps: adding siloxane resin and a dispersing agent into a charging basket, adding a part of solvent, stirring for 15min at a low speed by using a high-speed stirrer, adding pigment and filler raw materials after uniform dispersion, stirring for 30min at the rotating speed of 1200-1500 r/min, grinding until the fineness of the coating is below 30 microns after uniform dispersion, adjusting the viscosity to 200-800 cp by using the residual solvent, filtering and packaging after qualified detection.
The coatings prepared in the examples 1-3 and the comparative examples 1-2 are respectively sprayed on the surface of the carbon fiber composite board, the sprayed surface has no cracks, the thickness of the coating is about 10 mu m, a paint film is obtained after the coatings are completely cured, the paint film is placed at 800 ℃ for 1h, and the appearance and the adhesive force of the paint film are subjected to comparative tests. The results obtained are shown in Table 2.
Table 2: the high temperature resistant coatings prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to performance test results:
Figure BDA0003263718650000051
from the experimental results in table 2, the conventional silicone (siloxane) high-temperature resistant coatings in comparative examples 1-2 have no blistering, cracking and falling off at 800 ℃, but the silicone resin is carbonized at high temperature, so that the paint film has the phenomena of fading, bonding strength loss and falling off after scratching for hundreds of grids; the polysilazane high-temperature resistant coating in the embodiments 1 to 3 of the invention has a normal paint film and good high-temperature resistance at 800 ℃.
Finally, it should be noted that the above contents are only used to illustrate the technical solutions of the present invention, and do not limit the protection scope of the present invention. Simple modifications and equivalents may be made by those skilled in the art without departing from the spirit and scope of the present invention.

Claims (5)

1. A polysilazane high temperature resistant coating for carbon fiber composite material is characterized in that: the polysilazane high-temperature resistant coating for the carbon fiber composite material is composed of the following raw materials in parts by weight: 30-40 parts of organic silazane resin, 45-60 parts of butyl acetate, 12-20 parts of high-temperature resistant pigment, 2-5 parts of anti-settling agent, 1-2 parts of fumed silica and 1-2 parts of dispersing agent.
2. A polysilazane high-temperature resistant coating for carbon fiber composite according to claim 1, characterized in that: the polysilazane high-temperature resistant coating for the carbon fiber composite material is composed of the following raw materials in parts by weight: 32 to 38 portions of organic silazane resin, 48 to 55 portions of butyl acetate, 14 to 18 portions of high-temperature resistant pigment, 3 to 4 portions of anti-settling agent, 1.2 to 1.7 portions of fumed silica and 1.3 to 1.8 portions of dispersant.
3. A polysilazane high-temperature resistant coating for carbon fiber composite according to claim 2, characterized in that: the polysilazane high-temperature resistant coating for the carbon fiber composite material is composed of the following raw materials in parts by weight: 35 parts of organic silazane resin, 50 parts of butyl acetate, 16 parts of high-temperature resistant pigment, 3 parts of anti-settling agent, 1.5 parts of fumed silica and 1.5 parts of dispersing agent.
4. The method for preparing polysilazane high-temperature-resistant coating for carbon fiber composite according to claim 1, 2, or 3, characterized in that: the preparation method of the high-temperature resistant coating specifically comprises the following steps:
the method comprises the following steps: weighing the raw materials according to the weight parts of the components of the raw materials in the coating, then respectively placing the pigment and the filler in a dry and clean tray, placing the tray in a vacuum oven for drying, respectively bagging and sealing after natural cooling for later use, and carrying out corresponding identification;
step two: adding the organic silazane resin and the dispersing agent into a charging basket, adding part of the solvent, stirring for 15min at a low speed by using a high-speed stirrer, and adding the raw materials dried in the step one after uniform dispersion;
step three: stirring for 30min at the rotating speed of 1200-1500 r/min by using a stirrer, uniformly dispersing, grinding until the fineness of the coating is below 30 micrometers, adjusting the viscosity to 10-20 s by using the residual solvent, filtering and packaging after the viscosity is qualified.
5. The method for preparing polysilazane high-temperature-resistant coating for carbon fiber composite according to claim 4, comprising: and in the third step, the viscosity of the high-temperature resistant coating is detected by a coating-4 cup.
CN202111080275.7A 2021-09-15 2021-09-15 Polysilazane high-temperature resistant paint for carbon fiber composite material and preparation method thereof Pending CN113717639A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114395328A (en) * 2021-12-08 2022-04-26 赛纳化学(太仓)有限公司 High-hardness wear-resistant anti-sticking ceramic coating and preparation and use methods thereof
CN115231929A (en) * 2022-07-01 2022-10-25 库贝化学(上海)有限公司 High-temperature-resistant non-combustible fiber composite material and preparation method thereof
CN115819093A (en) * 2022-10-17 2023-03-21 杭州清瓷新材料科技有限公司 Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof

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CN105385349A (en) * 2015-12-10 2016-03-09 广州弘海化工科技有限公司 Hydrophobic and antifouling organic polysilazane coating, and preparation method and application thereof
CN109468065A (en) * 2018-11-02 2019-03-15 中国航发北京航空材料研究院 A kind of fire-resistant anticorrosion paint of ambient temperature curable
CN110373108A (en) * 2018-04-13 2019-10-25 中国科学院化学研究所 A kind of high-temperature insulation coating and its preparation method and application
CN110452615A (en) * 2019-08-30 2019-11-15 广东工业大学 A kind of high temperature resistant non-sticking lining and preparation method thereof
CN112063300A (en) * 2020-09-26 2020-12-11 库贝化学(上海)有限公司 Polysilazane high-temperature resistant coating and preparation method thereof
CN112300661A (en) * 2020-11-02 2021-02-02 刘超 High-temperature-resistant coating and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105385349A (en) * 2015-12-10 2016-03-09 广州弘海化工科技有限公司 Hydrophobic and antifouling organic polysilazane coating, and preparation method and application thereof
CN110373108A (en) * 2018-04-13 2019-10-25 中国科学院化学研究所 A kind of high-temperature insulation coating and its preparation method and application
CN109468065A (en) * 2018-11-02 2019-03-15 中国航发北京航空材料研究院 A kind of fire-resistant anticorrosion paint of ambient temperature curable
CN110452615A (en) * 2019-08-30 2019-11-15 广东工业大学 A kind of high temperature resistant non-sticking lining and preparation method thereof
CN112063300A (en) * 2020-09-26 2020-12-11 库贝化学(上海)有限公司 Polysilazane high-temperature resistant coating and preparation method thereof
CN112300661A (en) * 2020-11-02 2021-02-02 刘超 High-temperature-resistant coating and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114395328A (en) * 2021-12-08 2022-04-26 赛纳化学(太仓)有限公司 High-hardness wear-resistant anti-sticking ceramic coating and preparation and use methods thereof
CN115231929A (en) * 2022-07-01 2022-10-25 库贝化学(上海)有限公司 High-temperature-resistant non-combustible fiber composite material and preparation method thereof
CN115231929B (en) * 2022-07-01 2023-08-29 库贝化学(上海)有限公司 High-temperature-resistant incombustible fiber composite material and preparation method thereof
CN115819093A (en) * 2022-10-17 2023-03-21 杭州清瓷新材料科技有限公司 Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof
CN115819093B (en) * 2022-10-17 2023-10-24 杭州清瓷新材料科技有限公司 Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof

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